Certificate of correction



United States Patent Office 3,157,689 Patented Nov. 17, 1964 3,157,689CYANOETHYLA'IED AMINO HYDROXY NITRILES Edgar R. Rogier, Hopkins, Minn.,assignor to General Mills, Inc., a corporation of Delaware No Drawing.Filed Apr. 1, 1960, Ser. No. 19,170 8 Claims. (Cl. 260-4655) The presentinvention relates to the novel cyanoethylated amino hydroxy higheralkylnitriles and their substituted amino derivatives.

These compounds may be used for a large number of purposes such asplasticizers for polyvinyl resins, corrosion inhibitors, sludgeinhibiting additives for fuel oils, chemical intermediates, and thelike. In addition, these cyanoethylated amino hydroxy higheralkylnitriles serve as valuable intermediates in the production of novelhydroxy polyamines.

The novel compounds of the present invention are those cyanoethylatedamino hydroxy higher alkylnitriles which have the formula RCN in which Ris an aliphatic hydrocarbon group containing 8 to 24 carbon atoms andhas attached to each carbon atom of at least one pair of adjacent carbonatoms a different radical selected from the class consisting of OH and\CH2CH2CN where R is a member selected from the class consisting of (1)hydrogen, (2) aliphatic groups and (3) aryl groups.

The overall synthesis of these compounds may be illustrated by thefollowing series of reactions using oleic acid as a starting material:

CsH17CH=CH(CHz) COOH+NH C5H17CH=CH(CH2)7CN Pei-acetic Acid NH CQHHCHCH(CH2) 7CN CBHHCE /CH(CH2)7CN O H N H: O lACl'YlOllitl'llB Thoseunsaturated fatty nitriles prepared by the reaction of ammonia and anunsaturated fatty acid, such as oleic, erucic, eleostearic, linoleic,linoleuic, clupanodonic, palmitoleic and palmitolenic acid formconvenient starting materials for preparing epoxy nitriles which containan even number of carbon atoms. Those unsaturated fatty nitriles whichare prepared by the reaction of an unsaturated alkyl halide and aninorganic cyanide form convenient starting materials for preparing epoxynitriles which contain an odd number of carbon atoms.

The unsaturated fatty acids previously referred to occur naturally inanimal and vegetable fats and oils such as soybean, safliower,cottonseed, rapeseed, linseed and sardine oils and the like. Thepreviously mentioned unsaturated alkyl halides may be prepared byconverting one of the aforementioned fatty acids to an alcohol andreacting that alcohol with a halogen acid to form the alkyl halide.

It will be readily apparent to those skilled in the art that a largenumber of amino hydroxy nitriles may be prepared by reacting one of thepreviously described epoxy nitriles with ammonia or a primary amine. Thealiphatic primary amines containing 1 to 24 carbon atoms such asmethylamine, ethylamine, hexylamine, octylamine and stearylamine; thearyl amines such as the amino phenols; the hydroxyl alkyl aminescontaining 1 to 4 carbon atoms, such as the ethanolamines; and thepolyamines which contain primary amino groups such as propylene andethylene diamine, and the like are only representative of the manyvarieties of amine reactants which may be used to split the epoxy groupto form the amino hydroxy nitriles which will upon reaction withacrylonitrile yield the compounds of the present invention.

The epoxy ring may be split on either side of the oxygen bond so thatthe hydroxyl group or amino group may be attached to either of thecarbon atoms of the original epoxy group. Accordingly the reactionproduct may contain both isomeric forms of the compounds as illustratedby the following formulas which represent the compounds obtained when9,10-epoxystearonitrile is reacted with ammonia:

It will be apparent to those skilled in the art that the above mixtureof isomeric nitriles upon reaction with acrylonitrile will contain inaddition to the monocyanoethylated derivatives, 9-N-(cyanoethyl)amino-10- hydroxystearonitrile and its isomer 10-N-(cyanoethyl)amino-9-hydroxystearonitrile, some of the isomeric dicyauoethylatedcompounds 9-N-N-di(cyanoethyl) amino- IO-hydroxystearonitn'le and itsisomer 10-N,N-di(cyanoethyl) amino-9-hydroxystearonitrile. In contrast,when primary amines are used to split the epoxy ring, of course, onlythe monocyanoethylated compounds are obtained upon subsequentcyanoethylation.

While the exact conditions for the cyanoethylation may vary for thecompounds falling within the scope of the invention, it can generally besaid that the addition of the acrylonitrile to the available hydrogen ofthe amino group of the amino hydroxy nitrile proceeds satisfactorilywhen reacted in the presence of methanol at moderate temperatures (60 C.to C.) for varying periods of time (4 to 48 hours).

The present invention is further illustrated by the following examples.

EXAMPLE I 9 (1 0 -Amin0-1 0 (9) -Hydr0xystearonitrile An autoclave wascharged with 250 g. of 9,10-epoxystearonitrile (4.7% oxirane oxygen), g.of methanol and 166 g. of anhydrous ammonia. The reaction mixture wasthen agitated and heated at to C. for 9 hours at 750 p.s.i.g. pressure.After passing the crude reaction product through a sulfonic acid ionexchange resin in the acid form and vacuum distillation at 2 mm. Hg ayield of 163 grams of 9(10)-amino-10(9)-hydroxystearonitrile wasobtained which had and amine number of 186 (theoretical amine number forC H ON is 189).

9 (10)-(B-Cyan0ethyl) -Amino-10 (9) -Hydroxystear0- nitrile Into a 100ml. round bottom, 3-necked flask equipped with a thermometer, droppingfunnel, reflux condenser and magnetic stirrer was placed 50.0 g. of theabove prepared 9(l0)-amino-10(9)-hydroxystea.ronitrile and 5.0 g. ofmethanol. The resulting solution was heated to 75 C. and 9.8 g. ofacrylonitrile added, with stirring over a 5 minute period. The reactionmixture was heated to the reflux point (81 C.) and heated under gentlereflux until the pot temperature became constant at 88 C. (7 hours). Theunreacted acrylonitrile and the methanol were then removed by heating at90 C. under vacuum (13 mm.). The resulting 9(10)-(;3-cyanoethyl)-amino-10(9)-hydroxystearonitrile weighed 58.3 g. and had a total amine numberof 159 (calculated amine number for C21H39ON3 is EXAMPLE H 9(10)-Methylamin-10(9)-Hydr0xystear0nitrile Into a flask containing 350 g. of9,10-epoxystearonitrile (4.65% oxirane oxygen) was added 144 g. ofmethylamine and 100 ml. of methanol. The mixture was reacted at 150 C.for 4 hours. The catalyst and solvent were then removed as previouslydescribed, and the crude reaction product was distilled to yield9(10)-methylamino-10(9)-hydroxystearonitrile with an amine number of 182(calculated amine number for C H ON is 181).

9 (10) -N-(Cyan0ethyl) -Methylamin0-1 0(9) Hydroxystearonitrile Into a150 m1. round bottom, 3-necked flask equipped with a thermometer,dropping funnel, reflux condenser and magnetic stirrer was placed 75.4g. of the above prepared 9( 10) -methylamino- 1 0(9 -hydroxystearonitrile and 7.5 g. of methanol. The resulting solution was heated to75 C. and 19.5 g. of acrylonitrile added with stirring over a minuteperiod. The reaction mixture was then heated to reflux temperature andmantained at gentle re flux (85 C.) for 5 /2 hours. The unreactedacrylonitrile and the methanol were then removed by heating (90 C.)under vacuum (13 mm.).

The resulting 9 -N-(cyanoethyl) -methylamino-10 (9)-hydroxystearonitrileweighed 87.3 g. and had a total amine number of 158 (calculated for C HON i 154).

EXAMPLE III 9(10) -D0decylamino-10(9) -Hydr0xystear0nitrile Into a flaskcontaining 691 g. of 9,10-epoxystearonitrile (4.65% oxirane oxygen) wasadded 740 g. of ndodecylamine (amine number 303) and 124 g. of ethyleneglycol. The mixture was reacted for 8.8 hours at 150 C. After passingthe crude reaction product through a sulfonic acid ion exchange resin inthe acid form and subsequent vacuum distillation as described in ExampleI, a 92% yield as based on the weight yield of amine fraction andoxirane content of the 9,10-epoxystearonitrile of 91'0)-dodecyl-amino-10(9)-hydroxystearonitrile was obtained which had anamine number of 120 (calculated amine number for C H ON is 121).

9 (10) -N-(Cymi0ethyl) -D0decylamino10 (9) H ydroxyszearonz' trile Intoa round bottom, 3-necked flask equipped with a thermometer, droppingfunnel, reflux condenser and magnetic stirrer was placed 50.0 g. of theabove prepared 9(10)-dodecylamino-10(9)-hydroxystearonitrile and 9.2 g.of methanol. The resulting solution was heated to C. and 16.0 g. ofacrylonitrile added with stirring. The reaction mixture was then heatedto and maintained at gentle reflux C.) for 48 hours. The unreacted acrylonitrile and the methanol were then removed by heating the mixture atC. under vacuum (13 mm.).

The resulting 9 10) -N- (B-cyanoethyl -dodecylamino-10(9)-hydroxystearonit=rile weighed 101 g. and had an amine number of(calculated amine number for C33H63ON3 is EXAMPLE IV9(10)-Di-(;8-Cyan0ethyl)Amin0-10(9)Hydr0xystearonitrile Into a 500 m1.,r.b., 3-necked flask equipped with thermometer, reflux condenser andmagnetic stirrer was placed 100 g. of9(10)-,8-cyanoethylamino-10(9)-hyd-roxystearonitrile (amine number 25 g.acrylonitrile, 10 g. methanol (absolute) 6 g. glacial acetic acid and 2g. of 85% phosphoric acid. This reaction mixture was heated to thereflux point (78 C.) and maintained at that temperature for 96 hours.The reaction was then cooled and the mixture taken up in diethyl etherand washed with 5% sodium carbonate and finally three times with water.After drying, the solvent was removed by distillation and then heated at60 C. under high vacuum to remove unreacted acrylonitrile, methanol andwa- The product was purified by ion exchange methods. A styrenebutadiene methacrylate carboxylic acid ion exchange column was preparedcontaining 960 cc. resin or 1.64 equivalents capacity. This wasconverted from the ammonia form to the acid form with 10% aqueoushydrochloric acid. The resin was washed with water till Cl free, and wasthoroughly wetted with methanol. To this was charged 500 ml. of amethanol solution containing 46 g. of the above product. Methanol wasused to el-ute the resin and the efliuent methanol was collected in 500ml. portion-s and any organic matter recovered. The first eluatefraction (500 ml.) contained 0.5 g. nonmethanol organic material. Thenext 1000 ml. contained 29 g. of product shown to be9(10)-di-(fi-cyanoethylamino)-10(9)-hydroxystearonitrile. Approximately2 g. more was recovered from the succeeding 3000 ml. of eluate, and thiswas followed by 2000 ml. eluate containing no recoverable organic fattymaterials. Elution was begun with methanol containing 3% NH eventuallycollecting 17 g. of a second material in 4000 ml. of eluate.

The dicyano substituted amine had insuflicient base strength in thiscase to be picked up by the weakly acid carboxylic ion exchange resin.Consequently it passed through and the monocyanoethyl substituted aminewas exchanged by the resin and thereby separated. The purified dicyanoproduct 'had an amine number (HClO HOA of 133. After acetylation withacetic anhydride, the amine number was 135, indicating the product wasessentially the dicyano compound.

EXAMPLE V 9 (10) -Di-(fi-CyanoethyDAmino-l 0(9) -Hydr0xystearoni tril eA mixture of 160 g. of 9(10)-amino-10(9)-hydroxystearonitrile (aminenumber 188, mol. wt. 296, 0.54 mole), 60 g. acrylonitrile (1.13 mole),20 g. absolute methanol, 12 g. glacial acetic acid, and 4 g. of 85%phosphoric acid was heated in a 1000 ml. 3-necked r.b. flask withstirrer, condenser and thermometer. The reaction was maintained at 78 to82 C. throughout the 89 hour reaction period. The product was cooled,taken up in diethyl ether, and washed with sodium hydroxide solution andfinally with water. The solvent and unreacted acrylonitrile were removedat elevated temperatures under reduced pressure.

Sample 1, Sample 2, Sample 3, 15 hours 24 hours 89 hours Total Amine No153 151 141. 7

The embodiments of the invention which an exclusive 8, 1O N 3cyanoethyl) dodecylamino 9 hyproperty or privilege is claimed aredefined as follows: d t jt fle 1. 9-B-cyanoethy1-amino-10hydroxystearonitrile.

g. O-fllcyanoethyl-amigo-9-hydro1 ystearonitri1e. References Cited inthe file of this patent steagonibfle" cyan Y1) hYdIOXY 5 UNITED STATESPATENTS 4. 10 di (B cyanoethyl) amino 9 hydroxy 2,787,633 Hanrison eta1. Apr. 2, 1957 stearonitrile.

5. 9 -N p cyanoethyl) -methylamino lO-hy- OTHER REFERENCESdroxystearomtnle. 10 Bergmann: The Chemistry of Acetylene and Related d(ll y y methylammo 9 Compounds, 1948, p. 80.

roxys earomtn e. C h

7- 9 N (p cyanoethyl) dodecy amino 1O y 195 93 211131221 1613 The C em1sry of Acrylonitnle, 2nd ed.,

droxystearonitrile. a

UNITED STATES PATENT OFFICE Patent No. 3,157,689 November 1964 Edgar'R.'Rogier It is hereby certified'that error appears in the above numberedpatent requiring correction and that the said Letters Patent should readas corrected below.

Column 2, line 57, for "and" read an column 4, first table, in theheading to the second column, line 1 thereof,

11 H for C H ON read I C H ON Signed and sealed this 24th day of August1965,

(SEAL) A nest:

ERNEST W SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents UNITED- STATES PATENT OFFICE CERTIFICATE OF CORRECTION PatentNo. 3 ,157 ,689 November 17, 1964 EdgarR 'Rogie'r I It is herebycertifiedthat error appears in the above numbered pat- I ent requiringcorrection and that the said Letters Patent should read as correctedbelow.

Column 2, line 57, for "and" read an column 4, first table, in theheading to the second column, line 1 thereof,

n n for C H ON read C H ON Signed and sealed this 24th day of August1965.

(SEAL) A ttest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents UNITED- sTATEs PATENT OFFICE CERTIFICATE oF CORRECTION PatentNo. 3,157,689 November 17, 1964 Edgar'R. 'Rogier It is herebycertified'that error appears in the above numbered patent requiringcorrection and that the said Letters Patent should read as correctedbelow.

Coiumn 2, line 57, for "and" read an column 4, first table, in theheading to the second column, line 1 thereof,

f IIC n or H ON read C H ON Signed and sealed this 24th day of August1965a (SEAL) A nest:

ERNEST W. SWIDER EDWARD J. BRENNER Attcsting Officer Commissioner ofPatents

1. 9-B-CYANOETHYL-AMINO-10-HYDROXYSTEARNITRILE.